Production of nitrogen-containing anthraquinone bodies



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.To all ivbofmtt may concern:

Be it known that we, HUen ALBER'r En WARD Dnascrim and JOHN Tiioictas both" subjects ofthe King of Great Britain and lrelandfand both residing at Murrell Hill Works, Uarlisle, in the county of Cumberltl't'lCl E17Il dnd, have" invented certain hew and useil iillmpiovenients in and Relating to the Production of Nitrogen-Containing Anthraquinone Bodies, of which the following is a specification.

This invention relates to the production of derivatives of anthraquinone.

it isyspecitically directed totlie manufao ture of amino-derivatives of anthraquinone but includes intermediate products.

'lhe main object of the invention is to provide faprocess for the production of amen-derivatives of anthraquinone which are diiiicult to obtain by the present recognixed. processes.

investigat'ng a number oi? experiments and have found it halogen derivativeecf anthraquinone are treated i lth an irnide-oi a d'ibasic acid, such as phthalimide in the presence of copand. an -acid absorber, such as sodium acetate. at an e .evated temperature, the halogen is eliminated in the form of acid and a product isfitormed t'rcm the anth'raquinone body and stile ixnide. This product can be or example, with sulphuric acid so as to regenerate the diloasic acid and form an. ai'uindderirative of anthraquin'one.

We have feund that by this process we obtain amino-anthraquinoues which are ditlicult to secure by other means: "Among those which we have successfully convertedinto amino-derivatives may be cited l-chloranthraquinone, l 8-dichlor anthraq'uinone. 1-

anthraquinorie, l-chlor-5- itro-anthraquin- "We have also found that when the ins de cf the dibasic acid'will form .a. metal salt this be used instead ofthe imide; foreaarnple, the potassium derivative of phthalamide can be used instead oi phthahmlde.

'When. a. metal salt of annnide 15 used the presence of an acid absorber in the melt is i not necessary.

Uur invention consists in the treatment of a halogen derivative ianthraquinone with the inside of a dibasic acid in the presence of copper at a suitable temperature.

this matter we have inade Application iueiiamii as, 19214. Serial Ne-702,133.

References to the iniide eta dihasic acid in this specification and claims, except where the text otherwise requires, include a metal salt of such iinide, and'rclerences to copper similarly include copper in the metallic form or as a salt.

The invention also consists in the pr s- "r'ation oi: amino derivatives of authraqn ione b hydrolyzing an arnido derivative pre pare according to the method ct the ceding paragraph.

The inventicn further. consists in the par tial hydrolysis of an imide derivative prepared as described above for the producticn of a substituted benzoyl derivative.

The invention also consists in the prom essee and products hereinafter described.

Severalexemples are given below cit met.--' Ode of carrying the invention into eitect.

Example 1'.

quinone and its conversion into Laminaanthraquinone.

10 parts, or l-chlor-enthrsquinone. 'lpfi parts of phthalimide, parts sodi acetate and 0.1 part of copper h" suspended in 12.5 parts of ni heated to 200 C. The a stirred and is kept at this t period of 2 hours. The melt i: then all i to cool. The crude 1-phthaii quinone crystallizesout as yaile'ereu tale. These are filtered dried and washed with hot water. dried. The yield of l phthalirnide-authraquinone is 92% of the theoretical. The product can be recrystallized from nitrobenzcne.

parts of the condensation product are dissolved in parts of concentrated sulphuricacid and the mixture is heated to 100 C. for'one hour. After being; allowed to cool, the mixture is poured into water,

when 1--'am-ino-anthlaquinone separatss as a finely divided bright scarlet'solid, which is filtered oil, washed and dried. The yield of 'l-amino-antliraquinone from l-chlor-enthre. quinone by this process is ot the theoretical; I Ewample 9. a

This deals with the "production all Tl Vphthalimidohnthraquincne tram "l-chlec anthraquinone and its conversicn into l ammo-anthraqumone.

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10 parts of l-chlor-anthraquinone, 7.5 parts of phthalimide, parts of sodium acetate and 0.1 port of copper bronze are intimately mixed and heated to a temperature of from 200 to 210 C. for a period of four- (l. for a period of one hour, then allowed to cool and poured into water.

The product, l-amino-anthraquinone, separates out and 1s altered ofi, washed and dried.

Should there be any unchanged halogen derivative present this last treatnient vith sulphuric acid can he used as a. basis of separating the halogen derivative from the amino body, the concentration of the acid being first or all gradually reduced until all the halogen derivative is precipitated. The

melt is then poured into water andthc amino derlvative precipitated out and solated in the-usual way.

Emamplc 3.

This deals with the production of 1.5- diphthalimido-authraquiuone from 1.5-diclriouanthraquinone and its conversion into 1.5-diaminoanthraquinone.

parts of 1.5dichlor-anthraquinone, 11.8 parts of phthalimide, 9 parts of sodium acetate-and 0.1 part of copper bronze are suspended in 22 parts of nitrobenzene and heated to 195 C. with good stirring for a period of 2 hours. The mixture is cooled and the crystals of 1.5-diphthalimido-anthraquinone, which are deposited, are tiltered off, Washed and dried. The crude condensation product is purified by extraction with hot Water. It is then dried.

10 parts of the 1.o-diphthalimido authraquinone thus obtained are dissolved in parts of concentrated sulphuric acid andthe mixture is heated to to C. "for ,4

.I hour. Elt is then allowed to cool and poured ifuto water. 1.fi-diamino-anthraquinone separates out, and is filtered off, washed and dried.

Example .4.

This deals with the production of l-chlor 5- hthalimido anthraquinone from 1.5-dior-anthraqumone and lts conversion into I l-chlorwwamino-alithraquinone.

- product,

eases/e 10 parts of l.5dichlor authraquinone and 3.8 parts of sodium acetate are added to 4:3 parts of nitrobenzene. The mixture is heated to 170 with etlicientstirring. During a period of 1 hour, a. mixture of parts of phthalimide and 0.2 parts of copper bronze is added. The temperature is then raised to 175 C. and. kept at this for five hours. The melt is cooled, and when the crude l-chlor-5-phthaliiniddanthraquinone, has crystallized out, it is iiltered off, washed and dried. The crude product is purified by extraction with hot water.- It is then dried; 10 parts of this washed and driedcondensation productare added to 50 parts of concentrated sulphuric acid, and the mixture heated to 100 C. for one hour, then cooled and poured into water, filtered, washed and dried.

Alternatively, the cooled solution is diluted-hythe addition of 8.5 parts of water with good stirring. After cooling the mi);- ture. the solid deposited is filtered ofi.

washed and dried. The product is mainly 1-chlor-5-amino-anthraquiuoue.

In a similar way l-methyLamino-lamino-Q-brom-anthraquinone ma pared from 1-inethyl-amino-2-4libro-m-anthraquinone.

. Ewample 5.

This deals phthalimido-2-nitro-anthraeuinone from 1- sion into l-amino-Q-nitro-anthraquinone.

10. parts of 1-chlor-2-nitro-anthraquinono., d5 parts of phthalimide, 4.3 parts of sodium acetate and 0.1 part of anhydrous cupric chloride are added to 30 parts of nitiiobenzone and the mixture is Well stirred and heated to its boiling point. lit is kept gently boiling -for a period of 3 hours, and is then allowed to cool. When the crude product, 1- phthalimido-Q-nitro-apthraquinone has crystallized out, it is filtered ofl, washed and dried. It is then washedwell with hot water and again dried. 4

10 parts of this product tire added to: to parts of .conceutrated sulphuric acid and the miiiture warmed to 160 for a period of 'one hour, after which it is cooled and poured into water. The bright orange-red product which separftes out is' l-amino-QJ mtrdanthraquinoue. This is filtered o'fi, washed and dried. W

7 Example 6.

This deals with the production of 1- amino 2-methyl-4 -phthalimido-anthraquinone from 1-amino-2-methyl-et-lzrrorrm-anthraquinone and its conversion into diamino-2- methyl-anthrax uinone.

10 parts 0 1-aminoQ-methyl-d-bromoanthraquiuone, 5.8 parts of phthalimide, parts of sodium acetate and 0.1" part of an hydrous .cupric chloride are added to 30 be i with the production of 1- ,chlor-2-nitro-anthruquinone and its converand is removed by filtration. The product,

is Washed and dried.

Efrem/pk '1. deals with the production of ly w amino-kphthelimidoenthraquinone r 1 methyl amino 4 oroino anthraquinone and its conversion into l-methylamine--l-aminoenthraquinonc.

parts of l-methyhamino-ddiromoanthraquinone, parts of anhydrous eodium acetate, 18 parts of phthalimide and 0.32 part of copper bronze are suspended in parts of .nitrobeuzene and the mixture heated. with good stirring to a temperature of 216 C. for a period of'four hours. The melt, is then allowed to cool and when the "lliue product. l-methylun1ino-lphthulirnido-anthraquinone has" separated out it is filtered off, and the nitrohenzenc removed. This crude. product is extracted with hot Water and again Washed and dried. 10 parts of this product are added to parts of concentrated sulphuric acid and this mixture heated to 100 C. for a period of one hour. The mixture is allowed to cool is poured into Water and the solid, which separates out, is filtered off, Washed with. Water and dried. it consists Wholly or lar my of l-methyl-emino-d-aminc-anihraquinone.

Edd mp Z6 8.

this deals with the proddction of 1- ralimido-2-amino-unthraquinone from 1 chlor-2-amino-anthrsquinone and its convr: eion into l.2-diamino-anthraquinone 5.? parts of phthaliniide, 42 parts of sodiuin. acetate and 0.1 part of cupric chlorideare suspended in parts of nitrobcnzene and heated to 190495". The mixture is Well stirred and kept at this temperature While 10 parts or 1-cider-2-amino-anthraquinonc' 10 parts of the Washed and dried conheing cooled, the mixture itii poured into The product is crude 2-plithali1nido-anthru- VVhen the I product has crystallized out, it is filtered.

densation product are added to 40 parts of concentrated sulphuric acid, and the mixture heated to 100 C. for o iefhour. After Water and the 1.2-diamino-onthraquinone. which separates, us filtered off, washed and dried.

Era-mp1s 9.

This deals with the production of 2 phtlmlimido anthraquinoue from 2-hrom anthraquinoue and its conversion into 2- amidmanthrauuinono. It includes the preparation of 2*benzoyi-amido-anthruquinone- 2-carboxylic acid.

29 parts of 2-hroni-anthraquinone, 18.5 parts of phthalimide, 10 parts sodium acetate, 0.3 parts of copper ohloride'are suspended in 60 parts of nitrohenzene and heated with good stirring for several hours at. 2200" C.;i1nl5ll the reaction is com letc. It is cooled and filtered, the product reed from nitrohenzol, and the crude product extracted with hot Water, filtered and dried.

99 quinone. Any unchanged 2ln'om-anthruquinone contained in the crude 2-phthali- 1nido-anthriiquinonc thus obtained can be isolated by treating the product with cans tic soda. for cxan'iple, with 100 parts of a 0.5"? solution at the boil; this partially hydrolyzes the Q-phthalimido-anthraquinono to 2 henzoyl amide anthraquinone-EZcarhoxylic sioicl, and gives a soluble sodium salt leaving the Q-hronr-anthraquinone unaffected. On acidifying the filtrates. the 2-houzojzl-amido-anthraquinone2-carboxylicacid is precipitated; this can be filtered and dried.

For the preparation of 2-amido-anthruquinone, 10 parts of 2-phthalimido-anthra- 'quinone or of its defivatiue, Z-henzoylamido-anthraquinone-2}cerboxylic acid, are dissolved in 100. parts of concentrated sulphuric acid and warmed for. one hour at 90 to 100 C. The melt is then poured into Water, boiled, and the precipitated :Z-amidoanth'raquinone filtered off and dried.

Ealaoiple 10. This deals 1 with the producpion of 1;;

phhhalimido-anthraquinone from 'l-chlor an thraquinone and its conversion into 1-. amino-anthraquinone and is a modified form of Example 1. p

In this example 5 parts of l-chlor-anthraquinone are warmed with 10 parts of phthalimide 0.5 part of copper powder and 2 arts of fused sodium acetate. The mixture 18 Well powdered and melted together with stirring at. 200 to 250 C. for a short time until tests show that no more halogen derivative is present. The melt is then poured into Water, filtered-, washed from water" soluble material and dried. 1a

Mile lit consists of crude 1phthalimido-anthraq'uinone. dried product is dissolved in "ten its weight of sulphuric acid and kept lllll Q. for one hour, after which it is poured. into a large excess of water, filtered, washed and dried. it consists substantially of l--amino-anthraquinone.

Should there be any unchanged halogen derivative present, this last treatment with sulphuric acid can be used as a basis of scp mating the halogen derivative from the uznino body, the concentration of the acid being first of all gradually reduced until all the halogen derivative is precipitated. melt is then poured into water and the derivative precipitated out and isolated in the usual way.

I Example 11'.

This deals with the production of i-succinimido-anthraquinone from 1-chlor-a11- threquinone and its products of hydrolysis for example 1-axnino-anthraquinone.

parts of l-chlor-anthracpiinone, 5 parts at suc'cinimide, 4 parts of sodium acetate and 0.1 part of copper chloride are suspended in parts of nitrobenzeneand heated 185 C. with good stirring for a period of hours. and when the condensation product, namely, l-succinimidoenthraquinone, has separated as pale yellow crystals, the mother liquor is removed'end the product dried. This crude product may he purified by extraction with hot Water, filtration and drying.

During the above treatment part of the succininndo-euthraquinone is apparently hydrolyzed and a crop of the sodium salt of the resulting carooxylic acid can be obteined hy saiting out and cooling the water filtrates irom the aforesaid extraction, or

The mixture is allowed to cool alternatively by precipitation by acidifying and l-ainino-anthraquinone separates and may be filtered oil, washed and dried.

In the above hydrolysis, 10 parts of succininiido-anth 'aquinone can be replaced by 10 parts of its partially hydrolyzed deriva tive.

Having now described our invention,

what we claim as new and desireto secure by Letters Patent 1s I I 1. A method for the production of amino derivatives of anthraquinono which consists.

in the treatment of halogen derivatives of anthraquinone with an imide of a dihasic acid in the presence of copper followed by hydrolysis.

2. A method of producing anthrequinone I derivatives which comprises treating a halogen derivative of anthraquinone with an imide-of a dibasic acid in the presence of copper. i

Asia new intermediate, l-phthulimidoar hmquinonc, thesaine being a solid, solub e in hot nitrobenzene end orystallizing as pale yellow crystals, on cooling the solution, and not substantially affected by hot water, substantially as above described.

e. A method as, claimed in claim 1 in which the copper is in the form of a. bronze powder.

5. Anthraqu none derivatives by the process of claim 1.

In testimony whereof we names to this specification.

prepared have signed our HUGH ALBERT EDWARD DRESCHER. JOHN THOMAS. 

